The Correlation Between <Emphasis Type="Italic">f–f</Emphasis> Absorption and Sensitized Visible Light Emission of Luminescent Pr(III) Complexes: Role of Solvents and Ancillary Ligands on Sensitivity

The electronic absorption, excitation and sensitized visible light emission studies of three praseodymium (III) complexes: [Pr(fod)₃(bpy)], [Pr(fod)₃(phen)] and [Pr(fod)₃(bpm)]_n (fod = anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedione; bpy = 2,2'-bipyridyl, phen = 1,10-phenanthroline, bpm = 2,2'-bipyrimidine) in a series of non–aqueous solvents is presented. The f–f absorption transitions of Pr(III) are environment sensitive which is reflected by the change in the intensity (oscillator strength) and band shape (stark splitting) upon change in the solvent and/or the ligands. The sensitization of intense Pr(III) emission, in the visible region, of the complexes in solution upon excitation into the ligand centered π→π* absorption band is remarkable. The planar phen has pronounced impact and increases considerably the emission intensity of Pr(III) luminescence than the flexible bpy while bpm has been found least effective in promoting the emission intensity. The intensity of the f-f absorption and sensitized emission are correlated with the nature of the solvents. The donor solvent pyridine enhances the emission intensity of the [Pr(fod)₃(phen)] drastically and of [Pr(fod)₃(bpy)] marginally while the luminescent intensity of [Pr(fod)₃(bpm)]_n is decreased. The combined photophysical studies demonstrate that entry of the solvent molecule(s) to inner coordination sphere (complex–solvent interaction) is governed by the structure and basicity of the ancillary heterocyclic ligand attached to the Pr(III) complex. The strong donor DMSO transforms the three complexes into a similar species, [Ln(fod)₃(DMSO)₂], which results in similar electronic absorption and emission properties of the complexes in this solvent. The results demonstrate that highly luminescent praseodymium chelates can be designed with ligands containing suitable energy levels and their emission properties can be further modulated through suitable ancillary ligands and donor solvents, thus opening perspectives for applications in electroluminescent devices and luminescent probes.     

Novel deep centers for high-performance optical materials

Materials exhibiting strong optical emission also exhibit strong absorption at the same wavelengths because both emission and absorption are governed by the same optical dipole and density-of-states. Laser action requires a carrier injection large enough for emission to exceed absorption at laser wavelengths. Thus, strong self-absorption at luminescent wavelengths raises the operating current of LEDs, lasers, and optical amplifiers. Here we demonstrate that, contrary to conventional expectations, materials designed with novel deep centers achieve surprisingly large optical emission while, simultaneously, the inverse process of optical absorption remains very small. A striking consequence is that materials designed with our novel deep centers achieve transparency at a carrier injection which is four-orders-of-magnitude lower than in all technologically important semiconductors. Simultaneously, and surprisingly, our novel deep centers in GaAs achieve an optical gain, Einstein B coefficient, and radiative efficiency significantly larger than in direct-band-gap materials at 1.3–1.5 μm. We engineered this dramatic reduction of the injection to achieve transparency while retaining strong optical emission in our novel material by making use of a Franck–Condon shift of absorption away from luminescent wavelengths. PACS 71.55.Eq; 71.55.-i; 78.67.-n; 81.10.-h; 85.60.Jb     

Bremsstrahlung von Elektronen im Feld neutraler Atome

The process of deceleration of electrons by the field of neutral atoms is investigated by the aid of a model approximating the neutral atom by a constant potentialU in the interior of a sphere of radiusγ. The free-free emission coefficient is determined in the general case for an isothermal plasma; in the special case of an impenetrable sphere it is compared with the emission coefficient of the ion bremsstrahlung as obtained by the “soft” approximation. The results show that electron-atom radiation may not be neglegible as compared with electron-ion radiation, and this fact may be used to explain the experimentally observed increase of the emission coefficient with pressure which is more rapid than linear. This is verified numerically in the limiting case of an impenetrable sphere. In addition the bound-free absorption coefficient is determined both in general and in the special case of the H^? ion; a comparison is made with the absorption coefficient as obtained byChandrasekhar. By the aid of the method of “best approximation” given in the concluding part of the present paper the quantitiesU andγ may be determined for any neutral atom.     

含Cr3+透明微晶玻璃的发光性能

选择若干玻璃组成，制得了含莫来石晶相的透明微晶玻璃，利用吸收光谱和室温荧光光谱对玻璃和微晶玻璃的发光进行了研究。研究表明，在一定测试范围内提高玻璃的晶化温度可以提高Cr^3 离子的有效发光效率；Cr^3 离子浓度的增加使微晶玻璃的发光强度增加，但引起浓度淬灭，降低Cr^3 离子的有效发光效率。对微晶玻璃荧光光谱中688nm发射肩的成因进行了探讨，提出了微晶玻璃荧光光谱中688nm和700nm发射可能由^2E能级分裂引起的观点。     

稀土有机化合物的发光与能量传递

本文讨论了稀土有机化合物发光的能量传递过程;有机配位体的三重态相对于稀土离子的激发态的位置关系;形成三元配合物后对发光强度和谱带劈裂的影响;有机物中具有高能振动的含氢基团对荧光的猝灭作用;以及水分子的存在与采用不同的有机溶剂等因素对稀土发光的影响。文中还介绍了稀土有机发光材料的可能应用。     

Luminescent properties of a novel red-emitting phosphor: Eu-activated Ca3Sr3(VO4)4

A new luminescent material, Eu³⁺ activated Ca₃Sr₃(VO₄)₄, was investigated. This compound shows a strong red emission centered at 618 nm under near-UV light with two distinct absorption bands; charge transfer state of VO₄³⁻ and f-f transitions of europium ions. As the europium concentration is increased, an additional red-emitting phosphor, EuVO₄, which is known to be a prominent luminescent material in the near-UV region can be traced. The UV excited luminescent properties of this material may find application in the production of red phosphors for white light-emitting diodes.     

Optische und elektrische Erscheinungen in kupferaktivierten Natriumchloridkristallen

NaCl crystals activated with copper were prepared either from the melt or from an aqueous solution. They were coloured either photochemically or additively. The absorption, luminescence and electron emission were then measured on such crystals. The experimental results show the cause of the different results obtained by different authors and what conclusions can be drawn for the elaboration of models of luminescent centres.     

发光玻璃在X射线实时成像系统中的应用

介绍了以铽（Ｔｂ）激活的高密度发光玻璃和光导纤维发光玻璃的特性。它应用在Ｘ射线实时成像系统中,可大大改善空间分辨能力。用它做的转换屏比一般晶粒状荧光物质做的厚得多,特别适合用于高能Ｘ射线实时成像系统     

发光玻璃在X射线实时成像系统中的应用

 介绍了以铽(Tb)激活的高密度发光玻璃和光导纤维发光玻璃的特性。它应用在X 射线实时成像系统中,可大大改善空间分辨能力。用它做的转换屏比一般晶粒状荧光物质做的厚得多,特别适合用于高能X射线实时成像系统。     

Luminescence properties of europium (III) cryptates trapped in sol-gel glass

The Lanthanide complexes Eu-2.2.1 and Eu-2.2.2 were synthesized and then incorporated into silica based transparent organic-inorganic hybrid material by the sol-gel method as an example of how doped xerogel materials are emerging as an important means of producing new materials. The produced gels were diagnosed to monitor emission spectra of the luminescent trivalent europium (Eu³⁺) complexes; emissions were compared to those for gels containing uncomplexed Eu³⁺. Results of the experiments (emission and lifetimes) concerning the coordination sphere composition showed that a cryptand ligand with aromatic groups (short range effect) and the hydrophobic gel host (long range effect) settle efficient action in the antenna effect and isolate the central ion from efficient quenchers, as e.g. water molecules. Each ligand imposed a distinct splitting pattern on the europium emission bands that helps identify them.     

Luminescent properties of MBE-grown Si:Er/SOI structures

Here we report on luminescent properties of multilayer Si:Er structures grown by sublimation molecular-beam epitaxy on “silicon-on-insulator” substrates. We demonstrate formation in such structures of a unique erbium-related center Er-1. This optical complex stands out among other known erbium-related centers in silicon for its record narrow luminescent line (<10 μeV) and largest absorption cross-section and, therefore, provides the best conditions to achieve practically significant amplification and stimulated emission in erbium-doped silicon structures.     

非晶SiC_xO_y薄膜的可调强光发射机制

采用甚高频等离子体增强化学气相沉积技术,以SiH_4、CH_4和O_2作为反应气源,通过调控O2流量在250℃下制备强光发射的非晶SiC_xO_y薄膜。利用光致发光光谱、荧光瞬态谱、Raman光谱、X射线光电子能谱及红外吸收谱对薄膜的光学性质和微结构进行表征与分析,进而讨论其可调可见光发射机制。实验结果表明,SiC_xO_y薄膜发光性质与薄膜中的氧组分密切相关。随着薄膜中氧组分的增加,其发光峰位由橙红光逐渐向蓝光移动,肉眼可见强的可见光发射。荧光瞬态谱分析表明,薄膜的荧光寿命在纳秒范围。结合X射线光电子能谱和红外吸收谱对薄膜的相结构和化学键合结构进行分析,结果表明薄膜的主要相结构和发光中心随O_2流量的变化是其可调光发射的主要原因。     

Efficient red-emitting phosphor for near-ultraviolet-based solid-state lighting

Eu(3+) ion activated Y(2)MoO(6) synthesized by the sol-gel method had been investigated as an alternative red-emitting phosphor for solid-state lighting. Excitation spectra, emission spectra, and decay curves were measured to characterize the luminescent properties. The phosphor shows efficient absorption of near-ultraviolet (NUV) light, and it also exhibits excellent performance in emission intensity and color purity compared with the commercial phosphor in current use. This red-emitting material may be applied as a promising red component for the NUV excited white diode.     

Improving luminescent property of SrIn2 O4 :Eu3+ by co-doped A+ （A = Li, Na, K） or Sm3+

A series of SrIn2 O4 :Eu3+ phosphors are synthesized by a high temperature solid-state method, and their luminescent properties are investigated. They can be excited by 395-nm radiation, and produce red emission (619 nm); however, they have a low absorption of near-ultraviolet light with the wavelength of 400nm-405 nm. When co-doped with A+ (A=Li, Na, K), the emission intensity of SrIn2O4 :Eu3+ is significantly enhanced, but its emission and excitation spectral profile is unchanged. With co-doping Sm3+ , not only is the emission intensity of SrIn2 O4 :Eu3+ enhanced, but also the absorption is broadened and strengthened in the range of 400 nm-405nm. The effect of Sm3+ -doped content on the emission intensity of SrIn2O4 :Eu3+ , Sm3+ is investigated, and the optimal Sm3+ content is 0.02 mol.     

Effects of annealing on calcium tungstate crystals

The influence of annealing in different atmospheres on absorption and luminescent properties of high-quality undoped CaWO₄ single crystals is presented. The decreasing of green emission intensity after annealing in oxygen and air have been revealed, while two well-defined maxima near 25,000 and 32,000 cm⁻¹ can be observed in the induced absorption spectra. These maxima are attributed to the interstitial oxygen, possibly in the form of the O⁻-centre. The increase of the blue/green luminescence ratio has been revealed after annealing in nitrogen while the crystal transparency remains unaffected. The possible ways to reduce slow green emission component without changing crystal absorption are shown. Structure of colour centres and the models of revealed processes are discussed.     

1,10-菲啰啉-四氰基乙烯配合物发光性质的研究

基于探针在近年来得到发展,制备光学性能更为良好的发光材料成为当前化学工作者的研究热点,该工作预制备光学性能更为优良的新型发光材料,以满足人们日常生活及医疗等方面的需求。该工作以四氰基乙烯(TCNE)为第一配体,以1,10-菲啰啉(phen)为第二配体,通过分子间的电荷转移,合成1,10-菲啰啉-四氰基乙烯的电荷转移络合物,并对此反应机理进行初步探索。运用紫外光谱法、荧光光谱法和拉曼光谱法对配合物进行表征及发光性质的研究。比较配合物和配体的紫外吸收峰发现,配合物的吸收均源于配体1,10-菲啰啉的吸收,说明TCNE与Phen形成了稳定的络合物。同时分析荧光光谱,发现配合物的发射峰与配体四氰基乙烯相似,可认为配合物的荧光来自于配体的π—π*电子跃迁。从拉曼图谱中可以看出,在1 000~1 600 cm-1处配合物的拉曼强度比TCNE配体有明显的增强。共振拉曼散射在1 000~1 600 cm-1处振动模式被强耦合,由于分子间的电荷转移使得这些共振拉曼峰被强烈增强。分析结果表明,在一定条件下,1,10-菲啰啉能与四氰基乙烯形成稳定的络合物,且光学性能显著增强。上述研究,合成并研究了1,10-菲啰啉-四氰基乙烯荷移络合物的光学性质,为设计、合成荧光性能良好的配合物提供了实验依据, 并为探索和开发新的核酸探针做出了贡献。     

Transient Emission of Three-Level Atoms in a Photonic Crystal with a Pseudogap

We study the transient behaviour of an external field induced transient emission of three-level atomic systems embedded in a photonic crystal with a pseudogap. The expressions for fluorescence spectra and emission dynamics for luminescent materials in the pseudogap are obtained. The properties of the transient gain in the pseudogap are discussed. It shows that the transient emission in the pseudogap can be effectively controlled.     

席夫碱修饰的α-氰基二苯乙烯荧光液晶材料的合成与发光性质

为获得高效的发光液晶材料,将席夫碱结构单元引入α-氰基二苯乙烯体系,合成了(Z)-2-(4-((E)-4-丁氧基-2-羟基苯乙烯氨基)苯基)-3-(4-丁氧基苯基)丙烯腈(BHPA)。通过紫外-可见吸收光谱和荧光光谱,研究其聚集诱导发光增强(AIEE)性质;利用热重分析(TGA)、差示量热扫描(DSC)、偏光显微镜(POM)研究其热力学性质和液晶性质。结果表明,BHPA是具有AIEE特性的发光液晶材料,取向的BHPA膜具有发光各向异性,其线偏振度约为0.41。     

Influence of Yb~(3+) concentration on the upconversion luminescence of oxyfluoride material doped with Er~(3+)

In this paper,a new upconversion luminescent material co-doped with Erbium and Ytterbium is reported. The upconversion luminescence transition routes and related properties are studied. The results show that the absorption and emission intensities under excitation of 980 nm laser increase with the increase of the Yb3+ concentration. The red emission is stronger than the green emission. The energy transfer process plays an important role in the upconversion mechanism.